KR20220104700A - Fiber-reinforced thermoplastic composite sheet and manufacturing method thereof - Google Patents

Abstract

The present application relates to a fiber-reinforced thermoplastic composite sheet and a method for manufacturing the same. The fiber reinforced thermoplastic composite sheet has a marble texture effect on the surface obtained by laminating cut pieces of continuous fiber reinforced thermoplastic composite unidirectional tape, wherein the fibers and resin used in the continuous fiber reinforced thermoplastic composite unidirectional tape have different colors. Thermoplastic composite sheets can be manufactured using simple and rapid methods, meeting the individual requirements of the surface appearance of the final product.

Description

Fiber-reinforced thermoplastic composite sheet and manufacturing method thereof

The present invention relates to the field of composites. In particular, the present invention relates to a sheet of fiber-reinforced thermoplastic composite and a method for manufacturing the same.

Continuous fiber reinforced thermoplastic composites are composites of reinforcing fibers and a thermoplastic resin matrix produced by impregnating continuous fibers with a thermoplastic resin matrix under tightly controlled conditions. It is used in many fields such as automotive, aerospace, electrical and electronic, and mechanical fields due to its advantages such as high specific modulus, high specific strength, short molding cycle, and no chemical reaction during molding.

Fibers used to make continuous fiber reinforced thermoplastic composites mainly include carbon fibers, aramid fibers, and the like.

Carbon fiber (CF for short) is a high strength and high modulus special fiber with a carbon content greater than 90%. It is characterized by high temperature resistance, anti-friction, electrical conduction, heat conduction and corrosion resistance, etc., and is fibrous in appearance, soft, and can be processed into a variety of fabrics. Because its graphite microcrystalline structure is optimally oriented along the fiber axis, it has very high strength and modulus along the fiber axis direction. It also has high specific strength and high specific modulus due to its low density. Carbon fibers are mainly used as reinforcing materials to produce improved composites by mixing with resins, metals, ceramics, carbon, and the like. Among the existing engineering materials, the carbon fiber reinforced epoxy resin composite has the highest specific strength and specific modulus of elasticity.

With outstanding properties such as ultra-high strength, high modulus, high temperature resistance, acid and alkali resistance, light weight, insulation, anti-aging and long life cycle, aramid is widely used in fields such as composites, bulletproof products, building materials, special protective clothing and electronic equipment. widely used

Continuous fiber reinforced thermoplastic composites are mainly produced by methods including melt extrusion methods, film methods, solution methods or powder methods and the like. The melt extrusion method involves forming a composite by impregnating continuous fibers with a melt of a thermoplastic resin, which is characterized by complete impregnation and low cost. The film method involves placing continuous fibers between two layers of resin films to form a prepreg, then melting the resin at a suitable temperature, followed by pressing. The solution method generally involves preparing a low viscosity solution by dissolving the resin using a suitable solvent to produce a composite, impregnating the fibers with the resulting solution, and then volatilizing the solvent. The powder method is a method of manufacturing a prepreg by applying a powdery resin to a reinforcing material. The continuous carbon fiber reinforced thermoplastic composite unidirectional tape is also a kind of prepreg, in which the continuous carbon fibers are parallel to each other, and the unidirectional tape is generally 0.10 to 0.25 mm thick.

Current continuous fiber reinforced thermoplastic composites are mostly unidirectional or woven fibers combined with a colorless transparent thermoplastic. Its color and texture are relatively monotonous. Therefore, there is a need to develop more composites with different surface textures to produce customized products.

Patent application CN 109263050A discloses a fiber-reinforced composite having a wood grain effect and a method for producing the same. In this patent, the wood grain effect in the cross section is mainly achieved by using a thermosetting resin to prepare a composite material and cutting the material. This involves dipping a carbon fiber cloth or a glass fiber cloth in a first resin, preferably an epoxy resin; and coating one side of the carbon fiber cloth or glass fiber cloth dipped in the first resin in a semi-cured state with a colored second resin, wherein the second resin is preferably a two-component epoxy resin with an epoxy resin color paste and It is formed by blending with a diluent. repeating the above steps at a specific temperature and pressure until the laminate is formed and molded; Then, from the upper surface or the lower surface, the fibrous material having a wood grain effect is formed by cutting in a direction oblique toward the central axis direction perpendicular to the upper surface or the lower surface. This patent covers only thermoset resin composites that have a texturing effect in cross-section rather than top and bottom surfaces.

CN107443825A discloses a marble-like composite sheet comprising a TPU sheet layer, a fibrous material layer and a marble-like coating layer connected in turn. Through the arrangement of the marble-like coating layer, the marble-like composite sheet has the quality, luster and texture of natural marble. However, the marble-like texture of the marble-like composite sheet tends to disappear due to abrasion of the coating layer.

Accordingly, there is still a need in the art for a composite material having a permanent surface texture.

It is an object of the present invention to provide a composite material having a texturing effect on the surface.

Another object of the present invention is to provide a method for producing a composite material having a texturing effect on the surface.

Thus, according to the first aspect of the present invention, the composite sheet has a marble texture effect on the surface obtained by laminating cut pieces of continuous fiber reinforced thermoplastic composite unidirectional tape, wherein the fibers used in the continuous fiber reinforced thermoplastic composite unidirectional tape And a fiber-reinforced thermoplastic composite sheet is provided, characterized in that the resin has a different color.

According to a second aspect of the present invention,

I) cutting the continuous fiber reinforced thermoplastic composite unidirectional tape into pieces; and

II) tiling the resulting pieces in a mold and subjecting them to hot press molding to form a fiber reinforced thermoplastic composite sheet having a marble texture effect on the surface;

A method for manufacturing the fiber-reinforced thermoplastic composite sheet is provided.

The fiber reinforced thermoplastic composite sheet has a permanent marble texture effect on the surface and thus can be used in applications with surface appearance requirements, such as automotive interiors. Thermoplastic composite sheets can be manufactured using simple and rapid methods, meeting the individual requirements of the surface appearance of the final product.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will be described and explained in more detail below in conjunction with the drawings:
1 shows a carbon fiber reinforced thermoplastic composite sheet prepared from Example 1.
2 shows a carbon fiber reinforced thermoplastic composite sheet prepared from Example 2.

DETAILED DESCRIPTION OF THE INVENTION

Some embodiments of the invention are now described with reference to the drawings, for purposes of illustration rather than limitation.

According to a first aspect of the present invention, a composite sheet has a marble texture effect on its surface obtained by laminating cut pieces of a continuous fiber reinforced thermoplastic composite unidirectional tape, wherein the fibers and resins used in the continuous fiber reinforced thermoplastic composite unidirectional tape A fiber-reinforced thermoplastic composite sheet is provided, characterized in that it has different colors.

Preferably, the resin used in the unidirectional tape is polycarbonate (PC), thermoplastic polyurethane (TPU), polymethyl methacrylate (PMMA), polypropylene (PP), polyethylene terephthalate (PET) or a combination thereof. is selected from the group consisting of

Preferably, the fibers are selected from carbon fibers or aramid fibers. The fibers may be undyed or dyed.

In some embodiments, the fibers are undyed.

In some embodiments, the fibers are dyed prior to being used to reinforce the resin.

The resin used in the unidirectional tape may be unpigmented or pigmented.

In some embodiments, the resin used in the unidirectional tape is unpigmented and the fibers are undyed or dyed.

In some embodiments, the resin is pigmented and the fibers are undyed or dyed.

Preferably, the unidirectional tape has a thickness of 0.10 to 0.25 mm.

Preferably, the fibers in the unidirectional tape have a content by volume of 35% to 60%.

The fiber-reinforced thermoplastic composite sheet according to the present invention can be produced by a simple and rapid method.

According to a second aspect of the present invention,

I) cutting the continuous fiber reinforced thermoplastic composite unidirectional tape into pieces; and

II) tiling the resulting pieces in a mold and subjecting them to hot press molding to form a fiber reinforced thermoplastic composite sheet having a marble texture effect on the surface;

A method for manufacturing the fiber-reinforced thermoplastic composite sheet is provided.

Preferably, the unidirectional tape has a thickness of 0.10 to 0.25 mm.

Preferably, the fibers in the unidirectional tape have a content by volume of 35% to 60%.

Unidirectional tapes are commercially available or self-made.

Continuous fiber reinforced thermoplastic composite unidirectional tapes can be made by impregnating continuous fibers with resin. The impregnation method may be a method commonly used in the related art, for example, a melt extrusion method, a film method, a solution method or a powder method, etc., preferably a melt extrusion method.

In some embodiments, the method further comprises making the continuous fiber reinforced thermoplastic composite unidirectional tape by impregnating the continuous fibers with a resin.

The resins used in continuous fiber reinforced thermoplastic composite unidirectional tapes are polycarbonate (PC), thermoplastic polyurethane (TPU), polymethyl methacrylate (PMMA), polypropylene (PP), and polyethylene terephthalate (PET). It may be selected from the group consisting of.

If it is desired to obtain a sheet of fiber-reinforced thermoplastic composite in the form of a colored sheet, this can be achieved, for example, in a continuous fiber-reinforced thermoplastic composite unidirectional tape using colored fibers and/or colored resin in the production of a continuous fiber-reinforced thermoplastic composite unidirectional tape. It can be achieved by making it possible to exhibit a colored unidirectional tape, or by coating a continuous fiber reinforced thermoplastic composite unidirectional tape with a colored resin film.

In some embodiments, the continuous fiber reinforced thermoplastic composite unidirectional tape is a colored fiber reinforced thermoplastic composite unidirectional tape, and the method further comprises providing a colored continuous fiber reinforced thermoplastic composite unidirectional tape.

For example, in some specific embodiments, the unidirectional tape is a colored unidirectional tape, and the method further comprises using a continuous fiber and a resin to make the colored unidirectional tape, wherein at least one of the fiber and the resin is colored. do.

In some embodiments, the unidirectional tape is a colored unidirectional tape, and the method further comprises using a continuous fiber and a resin to make the colored unidirectional tape, wherein only the fibers are colored.

In some embodiments, the unidirectional tape is a colored unidirectional tape, and the method further comprises using a continuous fiber and a resin to make the colored unidirectional tape, wherein only the resin is colored.

In some embodiments, the unidirectional tape is a colored unidirectional tape, and the method further comprises using a continuous fiber and a resin to make the colored unidirectional tape, wherein both the fiber and the resin are colored.

In some embodiments, the method according to the invention comprises

I) impregnating the continuous fibers with a colored thermoplastic to form a continuous fiber reinforced thermoplastic composite unidirectional tape, wherein the fibers and the resin have different colors;

II) cutting the continuous fiber reinforced thermoplastic composite unidirectional tape obtained in step I) into pieces; and

III) tiling the pieces in a mold and subjecting them to hot press forming to form a fiber reinforced thermoplastic composite sheet having a marble texture effect on the surface;

includes

In some embodiments, the method according to the invention comprises

I) impregnating the colored continuous fibers with an unpigmented thermoplastic to form a continuous fiber reinforced thermoplastic composite unidirectional tape;

II) cutting the continuous fiber reinforced thermoplastic composite unidirectional tape obtained in step I) into pieces; and

III) tiling the pieces in a mold and subjecting them to hot press forming to form a fiber reinforced thermoplastic composite sheet having a marble texture effect on the surface;

includes

In some embodiments, the method according to the invention comprises

I) impregnating the colored continuous fibers with a pigmented thermoplastic to form a continuous fiber reinforced thermoplastic composite unidirectional tape, wherein the fibers and the resin have different colors;

II) cutting the continuous fiber reinforced thermoplastic composite unidirectional tape obtained in step I) into pieces; and

III) tiling the pieces in a mold and subjecting them to hot press forming to form a fiber reinforced thermoplastic composite sheet having a marble texture effect on the surface;

includes

In some embodiments, the method comprises, before cutting the unidirectional tape into pieces, covering one or both sides of the unidirectional tape with a colored resin film, laminating the unidirectional tape and the colored resin film by hot press molding, and then It involves cutting the unidirectional tape and the colored resin film together into pieces.

By introducing a colored resin film based on the original continuous fiber reinforced thermoplastic composite unidirectional tape, cutting it into pieces, and then hot pressing to form a fiber reinforced thermoplastic composite sheet with marble texture effect on the surface, different coloration It is possible to quickly screen the marble texture effect, save production cost, increase efficiency, and provide a reference solution for mass production.

The colored resin film is formed of a pigment-containing polycarbonate (PC), thermoplastic polyurethane (TPU), polymethyl methacrylate (PMMA), polypropylene (PP) or polyethylene terephthalate (PET) resin.

The colored resin film is commercially available or self-made.

Accordingly, the method according to the present invention may further comprise the step of preparing a colored resin film using the pigment-containing thermoplastic resin particles.

In some embodiments, the method according to the invention comprises

I) impregnating the continuous fibers with an unpigmented transparent or translucent first thermoplastic resin to form a continuous fiber reinforced thermoplastic composite unidirectional tape;

II) melt-extruding the pigmented second thermoplastic resin particles to form a colored resin film;

III) coating one or both sides of the continuous fiber reinforced thermoplastic composite unidirectional tape obtained in step I) with the colored resin film obtained in step II), and laminating the unidirectional tape and the colored resin film by hot press molding step;

IV) cutting the continuous fiber reinforced thermoplastic composite unidirectional tape coated with the colored resin film obtained in step III) into pieces; and

V) tiling the pieces in a mold and subjecting them to hot press forming to form a fiber reinforced thermoplastic composite sheet having a marble texture effect on the surface;

includes

There is no requirement for the order of the steps of forming the fiber reinforced thermoplastic composite unidirectional tape and forming the colored resin film.

Preferably, the first thermoplastic resin and the second thermoplastic resin are polycarbonate (PC), thermoplastic polyurethane (TPU), polymethyl methacrylate (PMMA), polypropylene (PP), and polyethylene terephthalate (PET). ) is independently selected from the group consisting of.

More preferably, the first thermoplastic resin and the second thermoplastic resin are the same type of resin.

Preferably, the colored resin film has a thickness of 0.04 to 0.10 mm.

A person skilled in the art can determine the temperature and pressure for hot pressing the unidirectional tape and the colored resin film, depending on the material used for the unidirectional tape and the colored resin film.

In some embodiments, the unidirectional tape and the colored resin film are laminated by hot press molding at a temperature of 170 to 180° C. and a pressure of 1 to 2 MPa.

The resulting piece may be of any shape, such as a rectangle, triangle or circle.

The resulting pieces may also have any suitable size.

For example, if the pieces are rectangular, they may have a length of 5 to 50 mm and a width of 5 to 50 mm.

If the pieces are triangular, circular or irregular, they may have a nominal size of 5 to 50 mm.

In this application, the nominal size refers to the size of the side length of a square having the same area as the piece.

A person skilled in the art can also determine the temperature and pressure for hot press molding of the piece, depending on the material used for the unidirectional tape and any colored resin film.

In some embodiments, the piece is hot press formed into a composite sheet at a temperature of 160 to 230 °C and a pressure of 1 to 5 MPa.

In some embodiments, the piece is hot press formed into a composite sheet at a temperature of 160 to 230° C. and a pressure of 2 to 3 MPa.

The descriptions of various features in the present application may be combined where there is no contradiction, all of which fall within the scope claimed by the present application.

As used herein, the terms "comprising" and "including" encompass situations that further include or encompass other elements not specifically recited, and situations consisting of the recited elements.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case the definition of a term in this specification conflicts with the meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, the definition set forth herein shall apply.

Unless otherwise specified, all numbers expressing quantities of ingredients, reaction conditions, etc. used in the description and claims are to be understood as being modified by the term "about." Accordingly, unless otherwise indicated, the numerical values and parameters set forth herein are approximations that may vary as necessary depending on the desired performance obtained.

Example

The concept, specific structure and technical effect of the present invention will be further described below in conjunction with the following examples and drawings so that those skilled in the art can fully understand the object, features and effects of the present invention. Those skilled in the art will readily understand that the examples herein are for illustrative purposes only and the scope of the present invention is not limited thereto.

equipment used

Name of pressing machine: Static hot pressing machine (model BL-6170-B) manufactured by Dongguan Baolun Precision testing Instrument Co., Ltd.

Example 1

A carbon fiber reinforced polycarbonate composite sheet was prepared according to the following steps:

First, continuous carbon fibers are impregnated with a white polycarbonate composition to form a continuous carbon fiber reinforced polycarbonate composite unidirectional tape having a thickness of 0.17 mm and a fiber content by volume of 44%;

Then, the resulting continuous carbon fiber reinforced polycarbonate composite unidirectional tape was cut into pieces having a size of 20 mm×10 mm;

Then, the pieces are tiled in a mold and they are subjected to hot press molding at a temperature of 170° C. and a pressure of 2 MPa for 10 minutes, so that a carbon fiber reinforced polycarbonate composite having a marble texture effect and a thickness of 1 mm on the surface forming a sheet.

A photograph was taken of the surface of the resulting carbon fiber reinforced polycarbonate composite sheet, and the photograph is shown in FIG. 1 .

Example 2

A carbon fiber reinforced polycarbonate composite sheet was prepared according to the following steps:

First, the continuous carbon fiber is impregnated with an unpigmented polycarbonate resin to form a continuous carbon fiber reinforced polycarbonate composite unidirectional tape having a thickness of 0.17 mm and a fiber content by volume of 44%;

Then, extruding the polycarbonate resin pellets containing the green pigment to form a polycarbonate film having a thickness of 0.04 mm;

The resulting polycarbonate film was coated on both sides of a continuous carbon fiber reinforced polycarbonate composite unidirectional tape, and the film and the unidirectional tape were bonded together at a temperature of 170° C. and a pressure of 2 MPa;

Then, the film and the unidirectional tape are cut into pieces having a size of 20 mm×10 mm;

Then, the pieces are tiled in a mold and they are subjected to hot press molding at a temperature of 170° C. and a pressure of 2 MPa for 10 minutes, so that a carbon fiber reinforced polycarbonate composite having a marble texture effect on the surface and a thickness of 1.05 mm forming a sheet.

A photograph of the surface of the resulting carbon fiber reinforced polycarbonate composite sheet was taken, and the photograph is shown in FIG. 2 .

Exemplary embodiments or examples of the invention have been described above, but are not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention will be encompassed within the scope of the claims of the present application.

Claims (15)

wherein the composite sheet has a marble texture effect on the surface obtained by laminating cut pieces of continuous fiber reinforced thermoplastic composite unidirectional tape, and the fibers and resins used in the continuous fiber reinforced thermoplastic composite unidirectional tape have different colors. Thermoplastic composite sheet. The resin according to claim 1, wherein the resin used for the unidirectional tape is polycarbonate (PC), thermoplastic polyurethane (TPU), polymethyl methacrylate (PMMA), polypropylene (PP), polyethylene terephthalate (PET) or A composite sheet selected from the group consisting of combinations thereof. The composite sheet according to claim 1 or 2, wherein the fibers are selected from carbon fibers or aramid fibers. The composite sheet according to any one of claims 1 to 3, wherein the fibers are undyed or dyed. The composite sheet according to any one of claims 1 to 4, wherein the resin used for the unidirectional tape is unpigmented or pigmented. 6. The composite sheet according to any one of claims 1 to 5, wherein the content by volume of fibers in the unidirectional tape is between 35% and 60%. I) cutting the continuous fiber reinforced thermoplastic composite unidirectional tape into pieces; and
II) tiling the resulting pieces in a mold and subjecting them to hot press forming to form a fiber reinforced thermoplastic composite sheet having a marble texture effect on the surface;
A method for manufacturing a fiber-reinforced thermoplastic composite sheet according to any one of claims 1 to 6, comprising a. 8. The method of claim 7, wherein the unidirectional tape has a thickness of 0.10 to 0.25 mm. 9. The method of claim 7 or 8, wherein the unidirectional tape is a colored unidirectional tape, further comprising using a fiber and a resin to prepare the colored unidirectional tape, wherein at least one of the fiber and the resin is colored. . The method according to claim 7 or 8, wherein, before cutting the unidirectional tape into pieces, one or both sides of the unidirectional tape are coated with a colored resin film, and the unidirectional tape and the colored resin film are laminated by hot press molding. and then cutting the unidirectional tape and the colored resin film together into pieces. The pigmented resin film according to claim 10, wherein the pigment-containing polycarbonate (PC), thermoplastic polyurethane (TPU), polymethyl methacrylate (PMMA), polypropylene (PP) or polyethylene terephthalate (PET) A method of forming with a resin. 12. The method according to claim 10 or 11, wherein the colored resin film has a thickness of 0.04 to 0.10 mm. The method according to any one of claims 10 to 12, wherein the unidirectional tape and the colored resin film are laminated by hot press molding at a temperature of 170 to 180°C and a pressure of 1 to 2 MPa. 14. The method according to any one of claims 7 to 13, wherein the pieces are rectangular, triangular or circular. 15. The method according to any one of claims 7 to 14, wherein the pieces are subjected to hot press forming to form a composite sheet at a temperature of 160 to 230 °C and a pressure of 1 to 5 MPa.

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